Patent GB-275292-A (GB)
Title: The manufacture of new vat dyestuffs containing sulphur
IPC: C09B7/00
Filed: 1926-04-09
Abstract: 275,292. Carpmael, W., (I. G. Farbenindustrie Akt.-Ges.). April 9, 1926. Thioindigoid dyes are obtained by condensing perinaphthoxypenthiophene or a nuclear substituted derivative thereof with a compound of the general formula where R is an aryl residue of the benzene or naphthalene series, R1 is a halogen atom or an arylido group, and Z is nitrogen; when the perinaphthoxypenthiophene contains an amino or acylamino, group in the o-position to the sulphur of the side chain, Z may also be sulphur (the bonds being displaced accordingly) and R, may he oxygen, Cl2, Br2. or an anil residue. 1- Halogen-2 : 3-naphthisatin-a-halogenides or arylides, or their further halogenated derivatives, and 2 : 3 - diketodihydro - 4 : 5 - benzo - 3 - oxythio - naphthenes or their 2-halides or 2-anils, or nuclear substitution products such as halogen derivatives, are particularly suitable. The dyestuffs from acidylaminoperinaphthoxypenthiophenes may be saponified for removal of the acidyl group. The products may be further halogenated and dye animal and vegetable fibres from the vat in fast blue to green shades. The following components are specified :-perinaphthoxypenthiophene, 2-amino- and 2-acetylamino; erinaphthoxypenthiophene (see Specification 234,928) ; the 4-acetylamino-, 2-benzoylamino-, 7-methoxy-2-acetylamino-, or 2-acetylamino-6. bromderivative of perinaphthoxypenthiophene : the chlorides of the 4 : 7-dichlor-, 4 : 6-dichlor-, 5 : 7-dichlor-, 4 : 5 : 6-trichlor-, 4-chlor-7-methoxy-, or 5-chlor-7-methylderivative of isatin; the a-chloride or the a-(1<1>-chlor-2<1>-naphthalide) of 1-chlor-2 : 3-naphthisatin (see Specifioation 21915/12), or its brominated derivative; 4: 5- benzo-2 : 3-diketodihydro-thionaphthene - 2 - (pdimethylamino)-anil and its 6-chlor-derivative; the 5-chlor-, 4-methyl-5-chlor-7-methoxy-, and 4 : 5 : 6-trichlor-derivatives of 2 : 3-diketodihydrothionaphthene-2-(p-dimethylamino)-anil. Perinaphthoxypenthiophenes substituted in the nucleus, for example by halogen, alkyl, alkyloxy, or acylamino, may be obtained from the curresponding substituted a-naphthalene sulphonic acids by conversion into the acid chlorides with phosphorus pentachloride or thionyl chloride, reduction to the mercaptans, condensation with chloracetic acid, and ring closure of the thioglycollic acids so obtained. The 2-aminoperinaphthoxypenthiophenes may be obtained by saponifying the 2-acylamino compounds. 2- Acylamino - 6 - bromperinaphthoxypenthiophenes may be obtained from 1. : 6-dibrom-2-aminonaphthalene by subjecting it to the series of reactions described in Specifications 17417/14 and 18292/14, acylating the 6-brnm-2-aminonaphthalene-1-thioglycollic acid, and subjecting the acylated products to ring closure, for example, by cold chlorsulphonic acid. 7-Methoxy-2-acetylaminoperinaphthoxypenthiophene may be similarly prepared from 2 : 7-aminonaphtholmethylether. 2: 3 - Diketodihydro - 4 : 5-benzo-6-chlorthionaphthene-2-(p-dimethylamino)-anil is obtained from a-naphthylamine by subjecting the latter to the series of reactions described in Specifications 17417/14 and 18292/14 and condensing the 4: 5- benzo-6-chloroxythionaphthene so produced with nitrosodimethylaniline. Isatin derivatives. - Brom-1-chlor-2 : 3-naphthisatin-a-(1<1>-chlor-2<1>-naphthalide) is prepared by condensing brom-1-chlor-2: 3-naphthisatin-achloride (Specification 21915/12) with 1-chlor-2- naphthylamine. 4 : 5: 6-Trichlorisatin is obtained from 3 : 4 : 5-trichloraniline by the method of Sandmeyer described in Specification 128,122; it yields the a-chloride in the usual manner 2 : 7-Aminonaphtholmethylether may be made from 2 : 7-naphthylamine sulphonic acid by alkali fusion, acetylation of the 2: 7-aminonaphthol, methylation with dimethylsulphate, and saponification of the acetylamino group.